KR20090033397A - Method for lubricating heavy duty geared apparatus - Google Patents

Abstract

A method for improving the oil drain interval, fuel and energy efficiency of heavy duty geared machinery by lubricating said apparatus using a lubricating oil composition comprising as base oil about 20 to 75 wt% PAO 2 to 10, about 5 to 40 wt% PAO 150-1000, about 10 to 40 wt% PAO 20-100, about 5 to 20 wt% of one or more polyol ester or dibasic acid ester having a kinematic viscosity of between about 2 to 5 mm2/s at 100 °C mm2/s and further containing an effective amount of at least one gear oil additive, said lubricating oil composition having a kinematic viscosity at 100°C between 9 and 12.5 mm2/s, and exhibiting a traction coefficient value (100°C/30 SSR value) of 0.0197 or less, a Brookfield viscosity at-40°C of about 26,000 cP or less a CCS viscosity at-25°C of 4200 cP or less, a flash point of 220°C or higher and a NOACK volatility of 15% or less.

Description

METHOD FOR LUBRICATING HEAVY DUTY GEARED APPARATUS}

The present invention relates to a method for improving the energy efficiency of a heavy load gear machine / device by using a power transmission fluid or gear oil, and an improved performance efficiency lubricant.

Heavy-duty gear machines, such as manual transmissions, automatic transmissions, differentials, gearboxes, etc., which are extended or operated under high temperature and heavy loads for extended periods of time, do not provide adequate film thickness, resulting in metal-to-metal contact (boundary lubrication). Current lubricating oil formulations are not properly lubricated.

Similar gear device manufacturers require that the lubricants used to lubricate the devices of the new design meet more stringent low temperature performance requirements in terms of Brookfield viscosity and cold cranking simulation (CCS) viscosity.

U.S. Patent No. 5,858,935 discloses a synthetic lubricating oil having 1 to 10mm kinematic viscosity ² / s at 100 ℃ natural mineral oils, more than 49% by weight having the same viscosity of 1 to 10mm ² / s at 100 ℃ of not more than 50% by weight and 1 An automatic transmission fluid comprising a high viscosity polyalphaolefin having a kinematic viscosity of from 40 to 500 mm ² / s at 100 ° C. of from 25% by weight.

In US Pat. No. 5,858,935, synthetic lubricating oils having kinematic viscosity at 100 ° C. of 1 to 10 mm ² / s are hydrocarbon oils and halo-substituted hydrocarbon oils such as multimerized olefins, polymerized olefins and interpolymerized olefins. (E.g. polybutene, polypropylene, propylene-isobutylene copolymer, polyactene chloride, poly (1-hexene), poly (1-octene), poly (1-decene) and the like and mixtures thereof), alkyl benzene It is mentioned that it can be chosen from polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, preferably polyalphaolefins. Additional synthetic lubricants include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof, various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, mono Tere, propylene glycol, etc.) and dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azlaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimers, Diesters which are esters of malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.), in particular dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, di- ahjeul isooctyl acrylate, isodecyl diamond ahjeul rate, dioctyl phthalate, di-decyl phthalate, di-eicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer chamber, preferably C ₄ -C ₁₂ It includes adipate call. Other useful synthetic lubricants include those made from C ₅ to C ₁₂ monocarboxylic acids and polyols and / or polyolesters such as neopentyl glycol, trimethylol propane, pentaerythritol and the like.

In general, preferred synthetic oils are referred to as polyalphaolefin diesters and polyol esters having a kinematic viscosity at 100 ° C. of 2 to 8 mm ² / s, preferably 3 to 5 mm ² / s.

U.S. Patent No. 6,713,439 discloses polyalphaolefin base stocks having kinematic viscosity of 1 to 49% by weight at 100 ° C of 40 to 500 mm ² / s, having kinematic viscosity of 1 to 95% by weight of 2 to 10 mm ² / s at 100 ° C. Lubricated base stock, polyol esters of polyol esters of 1 to 49% by weight of C ₅ to C ₃₀ aliphatic monocarboxylic acids with a general formula R (OH) n where n is 2 or more, and an effective amount of a performance additive package An energy conservation power transmission fluid, wherein the power transmission fluid composition has a kinematic viscosity of at least 4 mm ² / s at 100 ° C.

The lubricating base stock can be mineral oil or synthetic lubricating oil, preferably polyalphaolefin or mineral oil. In the case of polyol esters, the viscosity range is not given, and only Priiolube 3999 from Uniquea, Gouda, The Netherlands, has a kinematic viscosity of 13.19 mm ² / s at 100 ° C.

U.S. Pat.No. 5,089,156 discloses polyalphaolefin fluids having a kinematic viscosity of about 2 to 10 mm ² / s at a large amount of 100 ° C and polyalphaolefin fluids having a kinematic viscosity of about 40 to 120 mm ² / s at a small amount of 100 ° C. A lubricating oil composition comprising a dispersant and an antiwear / extreme agent selected from trivalent phosphorus- and boron-containing ashless dispersants, wherein the composition is free of metal-containing components and has a kinematic viscosity of at least 5.5 mm ² / s at 100 ° C. It is characterized by having a Brookfield viscosity of less than 20,000 cP at -40 ° C or having a kinematic viscosity of at least 6.8 mm ² / s at 100 ° C and a Brookfield viscosity of less than 50,000 cP at -40 ° C.

Formulations can also contain synthetic esters, such as mixed C ₉ and C ₁₁ dialkyl phthalates, trimethylol propane trioleate, di-isotridecyl-adipate, pentaerythritol tetraheptanoate, and the like. . The examples utilize PAO 6, PAO 8, PAO 110 and mixtures of diisononyl adipate, dioctyl sebacate, dibutyl phthalate or di (tridecyl) phthalate with performance additives.

U.S. Pat.No. 5,360,562 discloses polyalphaolefins having a kinematic viscosity of about 2 to 10 mm ² / s at 100 ° C of 70 to 99%, and a kinematic viscosity of about 40 to 120 mm ² / s at 100 ° C of 30 to 1% by weight. Automatic transmission, consisting entirely of polyalphaolefins, further containing 1 to 15% by weight of abrasion / extreme additives, other performance additives and up to 10% by weight of viscosity index improver, essentially free of metal-containing components With respect to a fluid, the fluid has a KV of at least 5.5 mm ² / s at 100 ° C and a Brookfield viscosity of less than ^20,000 cP at -40 ° C, or a KV of at least 6.8 mm ² / s at 100 ° C and at -40 ° C. It has a Brookfield viscosity of less than 50,000 cP. The fluid may also contain mixed C ₉ and C ₁₁ dialkylphthalates, trimethylol propane trioleate, di (isotridecyl) adipate, pentaerythritol tetraheptanoate, and the like. Examples include diisononyl adipate, di (tridecyl) adipate, Hatcol 2923, Hatcol 2920, Hatcol 2915, Synthetic Ester identified as Hatcol 2970, Dioctyl Sebacate, Dibutyl Phthalate, Dioctyl Sebacate A mixture of PAO 6 and / or PAO 8 + PAO 110 with Emery 2935 and Emery 2939 was used.

U.S. Patent No. 6,713,438 is selected from about 50-90% by weight mineral oil, polyalphaolefin, isomerized Fischer-Tropsch wax and has a base with a KV of 1.5-12 mm ² / s at 100 ° C. Oil, about 0.1 to about 20 weight percent of a first polymer (which is a polyalphaolefin having a lower molecular weight than the second polymer and a viscosity of 20 to 3000 mm ² / s) and about 0.1 to about 5 weight percent of a second It relates to high performance engine oils and other fluid lubricants comprising polymers, which have molecular weights of at least 100,000 and have viscosity thickening performance. In an embodiment, the, (4mm ² / s at ^{100 ℃) PAO, (5.6mm 2} / s at 100 ℃) PAO, PAO (150mm 2 / s at 100 ℃) (1.7mm ² / s at 100 ℃) PAO Various mixtures were blended with an "ester" which was prepared and unidentified. The low viscosity component may also include esters generally identified as having a kinematic viscosity at 100 ° C. in the range of 1.5 to 12 mm ² / s. The esters are derived from polyol esters of monobasic acids and dibasic acids reacted with monoalcohols. Useful esters include dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azalaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, Esters with various alcohols such as alkyl malonic acid, alkenyl malonic acid, for example butyl, hexyl, dodecyl, 2-ethylhexyl alcohol. Specific esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azate, diisodecyl azlate, dioctyl phthalate, didecyl phthalate , Diricosyl sebacate, and the like.

Useful polyol esters include one or more polyhydric alkals, preferably hindered polyols such as neopentyl polyols (eg neopentyl glycol, trimethylol ethane, trimethylol propane, 2-methyl-2-propyl-1,3 Propane diols, pentaerythritol and dipentaerythritol are prepared by reacting an alkanoic acid containing at least 4 carbon atoms, typically a C ₅ -C ₃₀ acid, Examples of such polyol esters are Mobil ) P-41 and Mobile P-51 esters (Mobile Chemical Company).

Published patent application US2003 / 0195128 relates to VI improved lubricating additives and lubricating oil compositions. The additive contains an olefin multimer having a number average molecular weight of about 2,000 to 20,000 and a viscosity of about 75 to 3,000 mm ² / s at 100 ° C., and at least about 5% of its weight from the aromatic moiety and from about 3 to about 100 ° C. Hydrocarbyl aromatic having a viscosity of 50 mm ² / s. Lubricants are disclosed to contain this additive. Such lubricants include base oils, which may be mineral oils, synthetic oils, or mixtures thereof, and synthetic oils include PAOs and esters as well as other possible synthetic materials. In the examples, the olefin multimer is a polymer of decene-1 having a viscosity of about 150 mm ² / s at 100 ° C., which has not been identified with PAO 4, mineral oil and KV, VI 131 of 5.5 mm ² / s at 100 ° C. Used in formulations containing unreacted esters (see Examples 4.2, 4.4 and 4.6).

Published patent application US2003 / 0207775 relates to lubricating fluid for automatic gears. The finished fluid has a viscosity index of at least 175.

The fluid comprises a polyalphaolefin blended with a lower viscosity fluid comprising a synthetic hydrocarbon, which may be a high viscosity fluid, preferably polyalphaolefin. High viscosity fluids have a KV of 40 to 3000 mm ² / s at 100 ° C., while lower viscosity fluids have a KV of 40 mm ² / s or less at 100 ° C. The blend may also contain one or more performance additives as well as esters and mineral oils. Examples include additives, lower viscosity hydrocarbon fluid PAO-2 (SHF ^™ 23), lower viscosity esters (Esterex ^™ M11), Supersin ^™ 2150 (PAO 150); A formulation comprising a mixture of an additive, PAO-25 (SHF ^™ 23), Esterex M11, SHF ^™ 1003 (PAO-100) (high viscosity hydrocarbon fluid), and Supercin 2300 (PAO 300) is presented. Esterex M11 is a commercially available ester having a kinematic viscosity at 100 ° C. in the range of about 1.25-1.45 mm ² / s.

Heavy-duty gears by identifying useful lubricant formulations in heavy-duty gear machines exhibiting improvements in traction coefficient during use, Brookfield viscosity at -40 ° C below about 21,000 cP and CCS at -25 ° C below about 3800 cP It would be advantageous to improve drainage spacing, fuel and energy efficiency of the machine.

Based on the total weight of the lubricating oil composition, from about 20 to 75% by weight, preferably from about 30 to about 60% by weight, more preferably from about 45 to 55% by weight, 2 to 10 mm ² / s, preferably Polyalphaolefin fluid having a kinematic viscosity (ASTM D-445-5) of 3.5 to 8 mm ² / s, more preferably about 3.5 to 6 mm ² / s; About 5 to 40% by weight, preferably about 5 to 20% by weight, more preferably about 8 to 12% by weight, 150 to 3000 mm ² / s, preferably 150 to 1500 mm ² / s, at 100 ° C Preferably polyalphaolefins having a kinematic viscosity (ASTM D-445-5) of about 150 to 1000 mm ² / s, even more preferably about 150 to 500 mm ² / s, most preferably about 150 to 300 mm ² / s Fluids; About 20 to 100 mm ² / s, preferably about 20 to 80 mm ² / s, at 100 ° C. of about 10 to 40% by weight, preferably about 15 to 30% by weight, most preferably about 18 to 22% by weight, More preferably a polyalphaolefin fluid having a kinematic viscosity (ASTM D-445-5) of about 20 to 60 mm ² / s, most preferably 40 to 60 mm ² / s; About 2 to 5 mm ² / s, preferably about 2 to 4.5 mm ² / s at 100 ° C. of about 5 to 20% by weight, preferably about 5 to 15% by weight, more preferably about 8 to 12% by weight , Mono-alkanols or mono of polybasic acids having a kinematic viscosity of more preferably about 2.5 to 4.5 mm ² / s and a pour point of at least -25 ° C, preferably at least -25 ° C, more preferably at least -45 ° C Esters of a mixture of alkanols and polyalkanols, or polyol esters, preferably non-polyol esters, more preferably esters of dibasic acids with mono alkanols, most preferably esters of adipic acid Further contains at least one gear oil additive; A traction coefficient value (measured as a 100 ° C./30 SSR value) at 100 ° C. having a KV of 9 to 12.5 mm ² / s, preferably 10 to 12 mm ² / s, of about 0.0197 or less, preferably about 0.0191 or less, A lubricating oil composition that exhibits a Brookfield viscosity of about 26,000 cP or less, preferably about 21,000 cP or less, and a CCS viscosity of about 4200 cP or less, preferably about 3600 cP or less, more preferably about 3400 cP or less at -40 ° C. A method has been developed to improve the fuel and energy efficiency of a heavy load machine under high load conditions by lubricating the heavy load gear machine using.

In the present invention, the base oil comprises specific combinations of polyalphaolefin base oils in combination with one or more of the mentioned esters, resulting in formulations that exhibit unpredictably improved performance characteristics.

Polyalphaolefins (PAO) are hydrocarbon base stock oils well known in the lubricating oil market. PAOs are derived by the polymerization or copolymerization of alphaolefins having 2 to 32 carbons, more typically C ₈ , C ₁₀ , C ₁₂ , C ₁₄ olefins or mixtures thereof.

PAOs that are known and commonly available on a commercial scale from suppliers such as ExxonMobil Chemical Company, Chevron-Phillips, BP-Amoco, Albermal Corporation, etc. The number average molecular weight of is typically varied from about 250 to about 3,000 or more, and may have a viscosity in the range of about 2 to about 3000 mm ² / s or more at 100 ℃.

PAO is typically relatively low molecular weight include hydrocarbons Chemistry The polymer or oligomer of an alpha-olefin, which does not include from about C ₂ to about C ₃₂ alpha olefins, however, this limitation, about C ₈ to about C ₁₆ alpha Preferred are olefins such as 1-octene, 1-decene, 1-dodecene and the like. Preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof, and mixed olefin-derived polyolefins. However, multimers of higher olefins in the range of about C ₁₄ to C ₁₈ may be used to provide low viscosity base stocks of acceptable low volatility. Depending on the viscosity grade and the starting multimer, PAOs are predominantly trimers and tetramers of the starting olefins and there may be small amounts of higher multimers.

PAO fluids are conveniently used for polymerization catalysts such as aluminum trichloride, boron trifluoride or boron trifluoride water, alcohols (eg ethanol, propanol or butanol), carboxylic acids or esters (eg ethyl acetate or ethyl propio) It can be prepared by polymerizing the alpha olefin in the presence of Friedel-Crafts catalyst including a complex with Nate). For example, the methods disclosed in US Pat. No. 4,149,178 or US Pat. No. 3,382,291 can be conveniently used herein. Other descriptions of PAO synthesis can be found in the following U.S. Pat.Nos. 4,956,122 and 5,068,487. Dimers of C ₁₄ to C ₁₈ olefins are disclosed in US Pat. No. 4,218,330.

High viscosity PAOs suitable for the present invention can be prepared by the activity of reduced chromium catalysts with alphaolefins, for example PAO, such PAOs are disclosed in U.S. Patent 4,827,073 (Wu) and U.S. Patent 4,827,064 (Ru) ), US Pat. No. 4,967,032 (Ho et al.), US Pat. No. 4,926,004 (Pelrine et al.), And US Pat. No. 4,914,254 (Pelin). Dimers of C ₁₄ to C ₁₈ olefins are disclosed in US Pat. No. 4,218,330. Commercially available high viscosity PAOs include Supercin ^™ 2150, Supercin ^™ 2300, Supercin ^™ 21000, Supercin ^™ 23000 (ExxonMobil Chemical Company).

In the present invention, the lubricating oil consists of a particular mixture of PAOs having different viscosities and includes an ester, and a base oil further containing one or more performance additives.

Lubricant formulations

(a) from about 20 to 75% by weight, preferably from about 30 to about 60% by weight, more preferably from 100 ℃ of about 45 to 55% by weight of 2 to 10mm ² / s, preferably, 3.5 to 8mm ² / O, most preferably PAO having a kinematic viscosity of about 3.5 to 6 mm ² / s;

(b) about 5 to 40% by weight, preferably about 5 to 20% by weight, more preferably about 8 to 12% by weight, at 150 ° C to 3000mm ² / s, preferably 150 to 1500mm ² / s, more preferably a PAO having a kinematic viscosity of about 150 to 1000 mm ² / s, even more preferably about 150 to 500 mm ² / s, most preferably about 150 to 300 mm ² / s;

(c) about 10 to 40% by weight, preferably from about 15 to 30% by weight, more preferably from 100 ℃ of about 18 to 22% by weight of about 20 to 100mm ² / s, preferably from about 20 to 80mm ² / O, more preferably PAO having a kinematic viscosity of about 20 to 60 mm ² / s, most preferably 40 to 60 mm ² / s;

(d) about 2 to 5 mm ² / s, preferably about 2 to 4.5 mm at 100 ° C. of about 5 to 20 wt%, preferably about 5 to 15 wt%, more preferably about 8 to 12 wt% Esters of mono-alkanols or mono-alkanols or mixtures of polyalkanols with mono- or polybasic acids having a kinematic viscosity of ² / s, more preferably about 2.5 to 4.5 mm ² / s, or polyol esters, preferably Are non-polyol esters, more preferably esters of dibasic acids with mono alkanols, most preferably esters of adipic acid

Including,

(e) additionally contains one or more gear oil additives,

The lubricating oil composition has a KV of 9 to 12.5 mm ² / s, preferably 10 to 12 mm ² / s at 100 ° C., and a traction coefficient value (100 ° C./30 SSR value) of about 0.0197 or less, preferably about 0.0191 or less. As measured), Brookfield viscosity of about 26,000 cP or less, preferably about 21,000 cP or less, and CCS viscosity of about 4200 cP or less, preferably about 3600 cP or less, more preferably about 3400 cP or less at -25 ° C. , 15% or less, preferably 13% or less of novol volatility and a flash point of 220 ° C. or higher, preferably 230 ° C. or higher,

All weight percentages are based on total lubricating composition.

In the text and the appended claims, kinematic viscosity is measured by ASTM D-445-5 test method, Brookfield viscosity at -40 ° C is measured by ASTM D-2983-31, cold at -25 ° C. Cranking simulation (CSS) viscosity is measured by ASTM D-5293-5, novol volatility is measured by ASTM D-5800, flash point is measured by ASTM D-97, and traction coefficient is 16N / 100C / 30SSR Is measured by.

The formulations of the invention are further distinguished in that there is no viscosity index improver whose presence is detrimental to the traction coefficient.

Esters of mono-basic and polybasic acids, in particular dibasic acids, with monoalkanols are dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, three Various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.) of baric acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, and the like, or Exemplified by its ester with polyalkanols). Specific examples of these types of esters are nonyl heptanoate, dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azate, diisodecyl Azlate, dioctyl phthalate, didecyl phthalate, diecosyl sebacate and the like.

Other useful synthetic esters include one or more polyhydric alcohols (preferably hindered polyols such as neopentyl polyols such as neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol , Trimethylol propane, pentaerythritol and dipentaerythritol) containing alkanes containing at least about 4 carbon atoms (preferably C ₅ to C ₃₀ acids, for example caprylic acid, capric acid, la) Saturated linear fatty acids, including uric acid, myristic acid, palmitic acid, stearic acid, arcic acid and behenic acid, or corresponding branched fatty acids or unsaturated fatty acids such as oleic acid). .

 Suitable synthetic ester components include esters with one or more carbon atoms of about 5 to 10 carbon atoms of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and / or dipentaerythritol.

Preferred esters are esters of dibasic acids with monoalkanols.

The gear oil formulation contains an effective amount of one or more gear oil performance additives. By effective amount it is meant that the additive is a small amount based on the total weight of the formulated lubricant sufficient to produce the desired performance change effect. The effective amount is generally at least about 20% by weight, preferably about 3 to 12% by weight, more preferably about 4 to 7% by weight of the at least one performance additive in total.

Suitable performance additives for use in the gear oils of the present invention to achieve desirable lubricating oil performance are antioxidants, antiwear additives, metal corrosion inhibitors, friction modifiers, ashless dispersants, detergents, antifoaming agents, seal swelling agents. . It is noteworthy that the gear oil formulation of the present invention is free of viscosity modifiers and viscosity index improvers.

Anti-wear and EP Additive

Many lubricants require antiwear and / or extreme pressure (EP) additives to provide adequate antiwear protection. For example, the increasing specification for engine oil performance has shown a trend towards improved sedimentation performance of oil. Anti-friction additives and polar additives perform this role by reducing friction and wear of metal parts, brass protection, thermal stability wear, wear damage, and surface fatigue.

While many different types of antiwear additives exist, for many decades the main antiwear additive for internal combustion engine crankcase oils is metal alkylthiophosphates, more particularly metal dialkyldithiophosphates, wherein the main metal component is zinc, or Zinc dialkyldithiophosphate (ZDDP). ZDDP compounds are generally Zn [Sp (S) (OR ¹ ) (OR ² )] ₂ , wherein R ¹ and R ² are C ₁ -C ₁₈ alkyl groups, preferably C ₂ -C ₁₂ alkyl groups Has the general formula These alkyl groups can be straight or branched chain. ZDDP is typically used in amounts of about 0.4 to 6% by weight, preferably about 0.8 to 4.0% by weight of the total lubricating oil composition, and higher or lower amounts may also often be used and the amount of phosphorus and zinc contributing to ZDDP is Preferably about 420-1500 ppm P and 450-1600 ppm Zn.

Various non-3 valent additives are also used as antiwear additives. Sulfurized olefins are often useful as antiwear and EP additives. Sulfur-containing olefins can be prepared by sulfur treating various organic materials, including aliphatic, arylaliphatic and acyclic olefin hydrocarbons of about 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. The olefin compound contains one or more non-aromatic double bonds. Such compounds are defined by the general formula R ³ R ⁴ C═CR ⁵ R ⁶ , wherein R ³ to R ⁶ are each independently hydrogen or a hydrocarbon radical. Preferred hydrocarbon radicals are alkyl or alkenyl radicals. Any two of R ³ to R ⁶ may be linked to form a cyclic ring. Further information on sulfurized olefins and their preparation can be found in US Pat. No. 4,941,984.

The use of thiophosphoric acid as a lubricating additive for polysulfides and thiophosphorous esters is disclosed in US Pat. Nos. 2,443,264, 2,471,115, 2,526,497 and 2,591,577. Anti-wear, anti-oxidation and addition of phosphorothionyl disulfide as an EP additive is disclosed in US Pat. No. 3,770,854. Alkylthiocarbamoyl in combination with molybdenum compounds (eg oxymolybdenum diisopropylphosphorodithioate sulfite) and phosphite esters (eg dibutyl hydrogen phosphite) as antiwear additives in lubricants The use of compounds (eg bis (dibutyl) thiocarbamoyl) is disclosed in US Pat. No. 4,501,678. US Patent 4,758,362 discloses the use of carbamate additives to provide improved wear resistance and extreme pressure properties. The use of thiocarbamates as antiwear additives is disclosed in US Pat. No. 5,693,598. Thiocarbamate / molybdenum complexes such as molly-sulfur alkyl dithiocarbamate trimer complexes (R═C ₈ -C ₁₈ alkyl) are also useful antiwear agents. The use or addition of such materials should be kept to a minimum if one wants to produce a low SAP formulation.

Esters of glycerol can be used as antiwear agents. For example, mono-, die and tri-oleate, mono-palmitate and mono-myristate can be used.

ZDDP can be combined with other compositions that provide abrasion resistance. U.S. Patent No. 5,034,141 discloses that the combination of a thiodixanthogen compound (e.g. octylthiodiixanthogen) and a metal thiophosphate (e.g. ZDDP) can improve wear resistance. U.S. Patent No. 5,034,142 discloses that the use of metal alkyloxyalkyl xanthates (eg nickel ethoxyethyl xanthate) and dizantogen (eg dieethoxyethyl diszantogen) in combination with ZDDP improves wear resistance. It is said to be possible.

Preferred abrasion resistant additives include various organic compounds including phosphorus and sulfur compounds such as zinc dithiophosphate and / or sulfur, nitrogen, boron, molybdenum, phosphorodithioate, molybdenum dithiocarbamate and heterocycles. It is a molybdenum derivative and can use, for example, acyclic, amine, alcohol, ester, diol, triol, fatty amide, etc., such as dimercaptothiadiazole, mercaptobenzothiadiazole, and triazine. Such additives may be used in amounts of about 0.01 to 6% by weight, preferably about 0.01 to 4% by weight. ZDDP-type compounds exhibit a significantly lower hydroperoxide resolution than the compounds disclosed and claimed herein exhibit, and are therefore minimal to facilitate the production of low SAP formulations, which may be removed or retained in the formulation. Maintained at a concentration.

Antioxidant

Antioxidants delay the oxidative degradation of the base oil during use. Such degradation can produce deposits on the metal surface, the presence of sludge or increased viscosity in the lubricant. Those skilled in the art know a wide variety of oxidation inhibitors useful in lubricating oil compositions. See, eg, Klamann, Lubricants and Related Products, and US Pat. Nos. 4,798,684 and 5,084,197.

Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of some phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols, which contain sterically hindered hydroxyl groups, which include derivatives of dihydroxy aryl compounds in which the hydroxyl groups are o- or p-position relative to one another. Typical phenolic antioxidants include the C ₆ of the hindered phenol and these hindered phenol substituted with an alkyl + alkylene coupled derivatives. Examples of this type of phenolic material are 2-t-butyl-4-heptyl phenol, 2-t-octyl-4-octyl phenol, 2-t-butyl-4-dodecyl phenol, 2,6-di-t- Butyl-4-heptyl phenol, 2,6-di-t-butyl-4-dodecyl phenol, 2-methyl-6-t-butyl-4-heptyl phenol and 2-methyl-6-t-butyl-4- Dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenol proprioric ester derivatives. Bis-phenolic antioxidants can also be advantageously used in combination with the present invention. Examples of ortho-coupled phenols are 2,2'-bis (4-heptyl-6-t-phenol), 2,2-bis (4-octyl-6-t-butyl-phenyl) and 2,2 ' -Bis (4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols are for example 4,4'-bis (2,6-di-t-butyl phenol) and 4,4'-methylene-bis (2,6-di-t-butyl phenol) Include.

Non-phenolic antioxidants that may be used include aromatic amine antioxidants, which may be used as such or in combination with phenolic. Typical examples of non-phenolic antioxidants include the following: alkylated aromatic amines and non-alkylated aromatic amines, for example R ⁸ R ⁹ R ¹⁰ N, wherein R ⁸ is aliphatic, aromatic or Is a substituted aromatic group, R ⁹ is an aromatic or substituted aromatic group, R ¹⁰ is H, alkyl, aryl or a general formula R ¹¹ S (O) _x R ¹² , wherein R ¹¹ is alkylene, alkenylene or Alkylene group, R ¹² is a higher alkyl group or an alkenyl, aryl or alkaryl group, x is 0, 1 or 2). Aliphatic groups R ⁸ may contain from 1 to about 20 carbon atoms and preferably contain about 6 to 12 carbon atoms. Aliphatic groups are saturated aliphatic groups. Preferably, R ⁸ and R ⁹ are both aromatic or substituted aromatic groups and the aromatic group may be a fused ring aromatic group, for example naphthyl. Aromatic groups R ⁸ and R ⁹ may be linked together with other groups such as S.

Typical aromatic amine antioxidants have alkyl substituent groups having about 6 or more carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Generally, aliphatic groups will not contain more than about 14 carbon atoms. Common types of amine antioxidants useful in the compositions of the present invention include diphenylamine, phenyl naphthylamine, phenothiazine, imidodibenzyl and diphenyl phenylene diamine. Mixtures of two or more aromatic amines are also useful. Polymerizable amine antioxidants may also be used. Polymerizable aromatic amine antioxidants include polymerizable diphenyl amine antioxidants, polymerizable phenyl naphthalene amine antioxidants and polymerizable diphenyl amine / phenyl naphthalene amine antioxidants. Specific examples of aromatic amine antioxidants useful in the present invention include p, p'-dioctyldiphenylamine, t-octylphenyl-alpha-naphthylamine, phenyl-alphanaphthyl amine and p-octylphenyl-alpha-naphthylamine It includes.

Sulfided alkyl phenols, alkali or alkaline earth metal salts thereof, alkyl aromatic sulfides, phosphorus compounds such as phosphites and phosphonic acid esters, and sulfur-phosphorus compounds such as dithiophosphates and other types such as dies Alkyl dithiocarbamates and mixtures thereof are also useful antioxidants.

Another class of antioxidants useful in lubricating oil compositions are oil soluble copper compounds. Any suitable oil soluble copper compound may be blended into the lubricant. Examples of suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphate and copper salts of carboxylic acids (natural or synthetic). Other suitable copper salts include copper dithiacarbamate, sulfonates, phenates and acetyl acetonates. Basic, neutral or acidic copper Cu (I) and / or Cu (II) salts derived from alkenyl succinic acids or anhydrides are known to be particularly useful.

Preferred antioxidants include arylamines which are hindered phenols. These antioxidants can be used individually by type or in combination with each other. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Detergent

Detergents are often used as lubricating compositions. Typical detergents are anionic materials containing the long chain hydrophobic portion of the molecule and the smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is typically derived from organic acids such as sulfuric acid, carboxylic acids, phosphorous acid, phenols or mixtures thereof. Counter ions are typically alkaline earth or alkali metals.

Salts containing substantially stoichiometric amounts of metal are disclosed as neutral salts and have a total base number of 0 to 80 (TBN, measured according to ASTM D2896). Many compositions are overbased by containing large amounts of metal bases obtained by reacting excess metal compounds (eg metal hydroxides or metal oxides) with acidic gases (eg carbon dioxide). Useful detergents may be neutral, mildly overbased, or very overbased.

It is desirable that at least some detergents be overbased. Overbased detergents help the acidic impurities produced by the combustion process to be neutralized and captured in the oil. Typically, the overbased material has a ratio of metal ion to anionic portion of the detergent on an equivalent basis of about 1.05: 1 to 50: 1. More preferably, the ratio is about 4: 1 to about 25: 1. The resulting detergent is typically an overbased detergent that will have a TBN of at least about 150, often at least about 250 to 450. Preferably, the overbased cation is sodium, calcium or magnesium. Mixtures of detergents having different TBNs can be used in the present invention.

Preferred detergents include alkali or alkaline earth metal salts of sulfonates, phenates, carboxylates, phosphates and salicylates.

Sulfonates can be prepared from sulfonic acids, typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Examples of hydrocarbons include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and halogenated derivatives thereof (eg chlorobenzene, chlorotoluene and chloronaphthalene). Alkylating agents typically have about 3 to 70 carbon atoms. Alkaryl sulfonates typically contain about 9 to about 80 carbon atoms or more, more typically about 16 to 60 carbon atoms.

Klamann, Lubricants and Related Products disclose a number of overbased metal salts of various sulfonic acids that are useful as detergents and dispersants in lubricants. See "Lubricant Additives", C.V. Smallheer and R.K. Smith, Lezius-Hiles Co. of Cleveland, Ohio (1967) similarly disclose a number of overbased sulfonates useful as dispersants / detergents.

Alkaline earth phenates are another useful class of detergents. These detergents are prepared by reacting alkaline earth metal hydroxides or oxides (eg CaO, Ca (OH ₂ ), BaO, Ba (OH) ₂ , MgO, Mg (OH) ₂ ) with alkyl phenols or sulfided alkylphenols. Can be prepared. Useful alkyl groups include straight or branched C ₁ -C ₃₀ alkyl groups, preferably C ₄ -C ₂₀ . Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol and the like. It should be noted that the starting alkylphenols may contain one or more alkyl substituents which are linear or branched independently of one another. If non-sulfurized alkyl phenols are used, sulfided products can be obtained by methods known in the art. These methods include heating a mixture of alkylphenols and sulfiding agents (including sulfur atoms, sulfur halides such as sulfur dichloride, etc.) and then reacting the sulfurized phenols with alkaline earth metal bases.

(여기서, R은 수소 원자 또는 1 내지 약 30개의 탄소 원자를 갖는 알킬 기이고, n은 1 내지 4의 정수이고, M은 알칼리토 금속이다)을 갖는 것이다. 바람직한 R 기는 C₁₁ 이상, 바람직하게는 C₁₃ 이상의 알킬 쇄이다. R은 세제의 기능을 방해하지 않는 치환체로 선택적으로 치환될 수 있다. M은 바람직하게는 칼슘, 마그네슘 또는 바륨이다. 보다 바람직하게는 M은 칼슘이다. Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents can be prepared by reacting a basic metal compound with one or more carboxylic acids and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful class of compositions is the general formula

Wherein R is a hydrogen atom or an alkyl group having from 1 to about 30 carbon atoms, n is an integer from 1 to 4 and M is an alkaline earth metal. Preferred R groups are C ₁₁ or higher, preferably C ₁₃ or higher alkyl chains. R may be optionally substituted with substituents that do not interfere with the detergent's function. M is preferably calcium, magnesium or barium. More preferably M is calcium.

Hydrocarbyl-substituted salicylic acid can be prepared from phenol by the Kolbe reaction. For further information on the synthesis of these compounds, see US Pat. No. 3,595,791, which is incorporated herein by reference in its entirety. Metal salts of hydrocarbyl-substituted salicylic acid can be prepared by double decomposition of metal salts in polar solvents such as water or alcohols.

Alkaline earth metal phosphates can also be used as detergents.

The detergent may be a simple detergent or one known as a hybrid or complex detergent. The latter detergent can provide the properties of the two detergents without the need to blend separate materials. See, for example, US Pat. No. 6,034,039.

Preferred detergents include calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate and other related compounds (including borated detergents). Typically, the total detergent concentration is about 0.01 to about 6.0 weight percent, preferably about 0.1 to 0.4 weight percent.

Supplementary Dispersant

During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help keep these byproducts in solution, thus reducing their deposition on metal surfaces. Dispersants may be ashless or ass-forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not substantially form ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, the metal-containing dispersants discussed above form ash upon combustion. As a supplemental dispersant use, non-borated ones of any of the dispersant types mentioned previously can be prepared. Such supplemental non-borated dispersants may be used in amounts of less than about 0.1 to 20 weight percent, preferably about 0.1 to 8 weight percent, based on the amount received.

Pour point depressant

Conventional pour point depressants (also known as lubricating oil flow improvers) may be added to the compositions of the present invention if desired. These pour point depressants can be added to the lubricating composition of the present invention to further lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. Terpolymers. U.S. Patent Nos. 1,815,022, 2,015,748, 2,191,498, 2,387,501, 2,655,479, 2,666,746, 2,721,877, 2,721,878, and 3,250,715 disclose useful pour point depressants and / or their preparation. have. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Corrosion Inhibitors / Metal Deactivators

Corrosion inhibitors are used to reduce degradation of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include triazoles and thiadiazoles, succinimide derivatives such as higher alkyl substituted amides of dodecylene succinic acid such as tetrapropenyl succinic acid monoester, and imidazoline succinic anhydride derivatives. Include. See, for example, US Pat. Nos. 2,719,125, 2,719,126, and 3,087,932. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Sealing Compatibility Additives

Sealing compatibility reagents help swell the elastomeric seal by causing chemical changes in the fluid or physical changes in the elastomer. Sealing compatibilizers suitable for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons and polybutenyl succinic anhydrides. Such additives may be used in amounts of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.

Antifoam

Advantageously an antifoam may be added to the lubricating composition. These reagents delay the formation of suitable foams. Silicones and organic polymers are typical antifoams. For example, polysiloxanes such as silicone oils or polydimethyl siloxanes provide antifoaming properties. Defoamers are commercially available and can be used in conventional minor amounts with other additives such as demulsifiers, and generally the amount of these additives combined is less than 1%, often less than 0.1%.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide range of these are commercially available, see Klamann, Lubricants and Related Products.

One type of antirust additive is a polar compound that preferentially wets the metal surface and protects it with an oil film. Another type of antirust additive incorporates water into the water-in-oil emulsion to absorb water so that only oil is in contact with the metal surface. Another type of anticorrosive additive chemically bonds to the metal to create a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Friction modifier

Friction modifiers are any materials that can change the coefficient of friction of surfaces lubricated by any lubricant or fluid containing such materials. Friction modifiers, also known as friction reducers or lubricants or oils, and other such reagents that change the ability to change the coefficient of friction of the surface on which the base oil, formulated lubricating composition or functional fluid is lubricated, are needed, It can be effectively used in combination with the base oil or lubricating composition of the invention. Friction modifiers that reduce the coefficient of friction are particularly advantageous when combined with the base oils and lubricating compositions of the present invention. Friction modifiers may include ash-free compounds or materials or mixtures thereof as well as metal-containing compounds or materials. Metal-containing friction modifiers may include metal salts or metal-ligand complexes where the metal comprises alkali, alkaline earth or transition group metals. Such metal-containing friction modifiers may also have low ash properties. The transition metal may include Mo, Sb, Sn, Fe, Cu, Zn and the like. The ligands are alcohols, polyols, glycerol, partial ester glycerol, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazias Hydrocarbyl derivatives of sol, dithiazole, diazole, triazole, and other polar molecular functional groups containing an effective amount of O, N, S or P individually or in combination. In particular, Mo-containing compounds such as Mo-dithiocarbamate, Mo (DTC), Mo-dithiophosphate, Mo (DTP), Mo-amines, Mo (Am), Mo-alcoholates, Mo-alcohols -Amides and the like can be particularly effective. For example, U.S. Pat. 6,569,820, WO 99/66013, WO 99/47629, and WO 98/26030.

Ashless friction modifiers may also include lubricating materials that contain effective amounts of polar groups, such as hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like. Polar groups in the friction modifiers may include hydrocarbyl groups containing an effective amount of O, N, S or P individually or in combination. Other friction modifiers that may be particularly effective are, for example, salts of fatty acids (both ash containing and ashless derivatives), fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates and comparable synthetic long chain hydrocarbyl acids, alcohols , Amides, esters, hydroxy carboxylates and the like. In some instances, fatty organic acids, fatty amines and sulfurized fatty acids can be used as suitable friction modifiers.

Useful concentrations of friction modifiers can be from about 0.01% to 10-15% by weight and often preferred ranges are from about 0.1% to 5% by weight. The concentration of molybdenum-containing material is often described as the Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, with about 20 to 2000 ppm being often the preferred range, and in some cases about 30 to 1000 ppm is the more preferred range. All types of friction modifiers can be used alone or as a mixture with the materials of the present invention. Often a mixture of two or more friction modifiers or a mixture of friction modifiers with other surface active materials is also preferred.

Dispersant

During mechanical operation, oil-insoluble oxidation by-products are produced. Dispersants help keep these byproducts in solution, reducing the deposition on the metal surface. Dispersants may be ashless or ash-forming in nature. Preferably the dispersant is ashless. So-called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, the metal-containing detergents discussed above form ash upon combustion.

Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

Chemically, many dispersants can be considered phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives. A particularly useful class of dispersants is the alkenylsuccinic acid derivatives which are typically produced by reaction of long-chain substituted alkenyl succinic compounds, generally substituted hydroxy succinic anhydrides with polyhydroxy or polyamino compounds. The long chain group constituting the lipophilic portion of the molecule that imparts solubility in oil is generally a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature. Exemplary US patents describing such dispersants are described in US Pat. No. 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,444,170; 3,454,607; 3,454,607; 3,541,012; 3,541,012; 3,630,904; 3,630,904; 3,632,511; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants include US Pat. No. 3,036,003; 3,200,107; 3,254,025; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,454,555; 3,565,804; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,449,250; 3,519,565; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 4,100,082; 5,705,458. Further description of the dispersant can be found, for example, in European Patent Application No. 471 071, to which reference is made for this purpose.

Hydrocarbyl-substituted succinic acid compounds are popular dispersants. Particularly useful are succinimides, succinate esters or succinate ester amides, preferably prepared by reacting a hydrocarbon-substituted succinic acid compound having at least 50 carbon atoms in a hydrocarbon substituent with at least one equivalent of alkylene amine. .

Succinimide is formed by the condensation reaction between alkenyl succinic anhydrides and amines. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1. Representative examples include US Pat. No. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; And 3,652,616, 3,948,800; And Canadian Patent 1,094,044.

Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, condensation products of alkenyl succinic anhydrides and pentaerythritol are useful dispersants.

Succinate ester amides are formed by the condensation reaction between alkenyl succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in US Pat. No. 4,426,305.

The molecular weight of alkenyl succinic anhydrides used in the above paragraphs will typically range from 800 to 2,500. The product may be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids (eg oleic acid) and boron compounds (eg borate esters or highly borated dispersants). The dispersant may be borated with about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

Mannich base dispersants are prepared from the reaction of alkylphenols, formaldehyde and amines. See US Pat. No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts such as oleic acid and sulfonic acid may also be part of the reaction mixture. The molecular weight of the alkylphenols is in the range of 800 to 2500. Representative examples include US Pat. No. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,756,953; 3,798,165; 3,798,165; And 3,803,039.

Typical high molecular weight aliphatic acid modified Mannich condensation products useful in the present invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenols, polybutylphenols, and other polyalkylphenols. These polyalkylphenols are benzene rings of phenols having an average molecular weight of 600 to 100,000 by alkylating phenols in the presence of an alkylation catalyst, for example BF ₃ , using high molecular weight polypropylene, polybutylene and other polyalkylene compounds. By producing an alkyl substituent on the phase.

Exemplary HN (R) ₂ group-containing reactants are alkylene polyamines, in principle polyethylene polyamines. Other representative organic compounds containing one or more HN (R) ₂ groups suitable for use in the preparation of Mannich condensation products are well known and are mono- and di-amino alkanes and substituted analogs thereof such as ethylamine and Diethanol amines; Aromatic diamines such as phenylene diamine, diamino naphthalene; Heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine; Melamine and substituted analogs thereof.

Examples of alkylene polyamine reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexaamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene decaamine And the nitrogen content corresponding to the alkylene polyamine in decaethylene undecaamine and the aforementioned general formula H ₂ N- (Z-NH-) _n H, wherein Z is divalent ethylene and n is 1 to 10 Mixtures of such amines having: Corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants. Alkylene polyamines are generally obtained by reaction of ammonia with dihalo alkanes, for example dichloro alkanes. Thus, alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkane of 2 to 6 carbon atoms and chlorine on other carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of high molecular weight products useful in the present invention include aliphatic aldehydes such as formaldehyde (also paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or formaldehyde-generating reactants are preferred.

Hydrocarbyl substituted amine ashless dispersant additives are well known to those skilled in the art and are described, for example, in US Pat. No. 3,275,554, which is incorporated herein by reference in its entirety; 3,438,757; 3,565,804; 3,565,804; See 3,755,433, 3,822,209 and 5,084,197.

Borated dispersants may be used. Any dispersant containing one or both of nitrogen and / or oxygen atoms can be borated.

Preferred dispersants include borated succinimides and non-borated succinimides and include those derived from mono-succinimides, bis-succinimides and / or mixtures of mono- and bis-succinimides. Wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene or a mixture of such hydrocarbylene groups having a Mn of about 500 to about 5000. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, capped derivatives thereof, and other related components. Such additives may be used in amounts of about 0.1 to 20% by weight, preferably about 0.1 to 8% by weight.

Amount of typical additives

If the lubricating oil composition contains one or more of the additives discussed above, the additive is blended into the composition in an amount sufficient to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table 1 below.

It should be noted that many additives are shipped from the manufacturer and used with a certain amount of base oil solvent in the formulation. Thus, the amounts indicated by weight in the following table, as well as the other amounts mentioned in the present patent, relate to the amount of the active ingredient (ie, the non-solvent portion of the ingredient), unless otherwise indicated. The weight percentages disclosed below are based on the total weight of the lubricating oil composition.

Typical amount of various lubricant components compound Approximate weight percent (useful amount) Approximate weight percent (preferred) Detergent 0.01 to 6 0.01 to 4 Dispersant 0.1 to 20 0.1 to 8 Friction reducer 0.01 to 5 0.01 to 1.5 Antioxidant 0.0 to 5 0.0 to 1.5 Corrosion inhibitor 0.01 to 5 0.01 to 1.5 Anti-wear additive 0.01 to 6 0.01 to 4 Pour point depressant 0.00 to 5 0.01 to 1.5 Antifoam 0.001 to 3 0.001 to 0.15 Base oil Remainder Remainder

The present invention is demonstrated by the following non-limiting examples and comparative examples.

The following examples and comparative examples are gear oils that meet the nominal grade 30 viscosity goal, unless otherwise indicated.

Traction coefficient is measured using the Mini Traction Machine, an accurate computer-controlled traction measurement system. A small amount of fluid sample is placed in the test cell and the machine is automatically operated at a range of speeds, slide / roll ratios, temperatures and loads to create a comprehensive traction map for the test fluid without any operator intervention. MTM can be tested using different sample arrangements, but the standard test samples used herein are polished 19.05 mm (3/4 inch) balls and 50.0 mm diameter discs made of AISI 52100 bearing steel. Samples are designed to be used once and discarded. The sample is independently driven by a DC servo motor and driven to allow high accuracy speed control, in particular low slide / roll ratio. Each sample is end mounted on a shaft in a small stainless steel fluid bath. The vertical shaft and the drive system supporting the 50 mm diameter test sample are fixed. However, the shaft and drive system supporting the 19.05 mm diameter test specimen are supported by the gimbal arrangement so as to be able to rotate around two diagonal axes. One axis is perpendicular to the load application direction and the other axis is perpendicular to the traction force direction. The load and restraint of traction is applied through a high-strength force transducer appropriately mounted in the gimbal arrangement to minimize overall support system deflection. The output from these force transducers is directly monitored by a personal computer (PC). The test conditions used herein were as follows: 16N load, 100 ° C. temperature and 30% slide to roll ratio (16N / 100 ° C./30 SSR).

Comparative Examples 1, 2 and 3 while using an adipate ester having a KV of 5.1 to 5.5mm ² / s at 100 ℃, Comparative Example 4 is adipate ester in 100 ℃ has a KV of 5.1 to 5.5mm ² / s Is still used but differs in that it uses other additive packages.

The inventive formulations of Examples 1 and 2 use the same base stock combination and additive package of PAO as Comparative Examples 1, 2, 3, 6 and 7, but differ in the properties of the esters used, and Example 1 A polyol ester having a KV of 4.2 to 4.5 mm ² / s at 100 ° C., a pour point of less than -45 ° C., and Example 2 has a KV of 2.7 mm ² / s at 100 ° C., of a pour point of less than -45 ° C. Use adipate (diester).

In both cases, the inventive oils of Examples 1 and 2 demonstrate unexpected improvements in both low temperature viscometer properties and traction coefficients. Brookfield viscosities at −40 ° C. of Examples 1 and 2 were 25,747 cP and 20,546 cP, respectively, CCS viscosities at −25 ° C. were 4118 cP and 3,357 cP, respectively, and traction coefficients were 0.01969 and 0.01945, respectively. Flash points are 242 and 234 ° C., respectively, and NOACK volatility is 9.0 and 12.7%, respectively. This improvement in low temperature viscosity and traction coefficient, while maintaining acceptable NOACK volatility and flash point, could not be predicted from this minor change in viscosity of the ester used in combination with the mixed PAO base stock.

Comparative Example 5 is 5.1 to 5.5mm ² / s of the adipate in 100 ℃ 2.8 to 2.9mm ² / s of KV, Moline (Emoline) the reported as having a pour point of less than -45 ℃ 2958 (Dai -2 Similar to Comparative Example 4, except that it is substituted with -hexyl adipate. Comparative Examples 6 and 7 are similar to Comparative Examples 1, 2, and 3, except that adipates (diesters) of 5.1 to 5.5 mm ² / s are respectively esterex (trade name) M31 (ethyl hexyl palmitate mono ester, at 100 ℃ 2.7mm pour point of KV, 3 ℃ of ² / s) and ester M11 Rex (nonyl heptanoate monomethyl ester, the literature value: from 100 ℃ 1.25 to 1.45mm ² / s of KV, a pour point of less than -45 ℃ ).

Although the blends of Comparative Examples 6 and 7 exhibited CCS viscosity and traction coefficients, and for Comparative Example 7, Brookfield viscosity met the specification goals of the present invention, they were not desirable from a practical point of view when used in real working environments. Proved insufficient. The formulation of Comparative Example 6 exhibited high Brookfield viscosity, which was completely unsatisfactory, while the formulation of Comparative Example 7 showed unsatisfactory flash point and NOACK volatility. Comparative Example 5 was produced with a KV outside the target of 9 to 12.5 mm ² / s, even when the preferred KV diester was used, when the combination of PAO base stock did not correspond to that mentioned in the present invention. It is demonstrated that the formulated oil exhibits an unacceptable Brookfield viscosity, an unacceptable CCS viscosity, and does not achieve the desired traction coefficient.

Claims (34)

Polyalphaolefin (PAO) fluid having a kinematic viscosity of about 2 to 10 mm ² / s at 100 ° C. about 20 to 75 wt%, polyalphaolefin fluid having a kinematic viscosity of about 150 to 3000 mm ² / s at 100 ° C. about 5 to 40 At least one polyalphaolefin fluid having a kinematic viscosity of about 20 to 100 mm ² / s at 100 ° C., about 10 to 40% by weight, at least one having a kinematic viscosity of about 2 to 5 mm ² / s at 100 ° C. and a pour point of at least −25 ° C. Comprising about 5 to 20 weight percent of a polyolester or diester, and additionally containing one or more gear oil performance additives, A traction coefficient of 9 to 12.5 mm ² / s at 100 ° C. and a traction coefficient of less than about 0.0197 when measured as a 16N / 100 ° C./30 SSR value, Brookfield less than or equal to about 26,000 cP at −40 ° C. Viscosity, CCS viscosity of about 4200 cP or less at -25 ° C, flash point of 220 ° C or higher, and NOACK volatility of 15% or less By using a lubricating oil composition, it involves driving a heavy duty gear machine under high load conditions while lubricating a heavy duty gear machine operating under high load conditions. How to improve fuel economy and energy efficiency of heavy duty gear machines operating under high load conditions. The method of claim 1, About 30 to 60 weight percent PAO fluid having a kinematic viscosity of about 3.5 to 8 mm ² / s at 100 ° C, about 5 to 20 weight percent of PAO fluid having a kinematic viscosity of about 150 to 1500 mm ² / s at 100 ° C ℃ to about 20 to PAO fluids of about 15 to 30% by weight, further comprises a ester of about 5 to 15% by weight having a kinematic viscosity of about 2 to 4.5mm ² / s at 100 ℃, and having a kinematic viscosity of 80mm ² / s at A method containing at least one gear oil performance additive. The method of claim 1, Wherein the lubricating oil composition comprises about 30 to 60 weight percent of a PAO fluid having a kinematic viscosity of about 2 to 10 mm ² / s at 100 ° C. The method of claim 1, Wherein the lubricating oil composition comprises about 5-20% by weight of a PAO fluid having a kinematic viscosity of about 150-3000 mm ² / s at 100 ° C. The method of claim 1, Wherein the lubricating oil composition comprises about 15-30% by weight of a PAO fluid having a kinematic viscosity of about 20-100 mm ² / s at 100 ° C. The method of claim 1, The ester comprises about 5-15 weight percent of the lubricating oil composition and has a kinematic viscosity of about 2 to 4.5 mm ² / s at 100 ° C. The method according to any one of claims 1 to 6, About 45 to 55 weight percent PAO fluid having a kinematic viscosity of about 3.5 to 6 mm ² / s at 100 ° C, about 8 to 12 weight percent of PAO fluid having a kinematic viscosity of about 150 to 1500 mm ² / s at 100 ° C And about 18 to 22 weight percent PAO fluid having a kinematic viscosity of about 20 to 60 mm ² / s at < RTI ID = 0.0 > The method of claim 7, wherein The ester is a non-polyol ester. The method of claim 8, The non-polyol ester comprises about 5 to 15 weight percent of the lubricating oil composition and has a kinematic viscosity of about 2.5 to 4.5 mm ² / s at 100 ° C. The method according to any one of claims 1 to 6, And the lubricating oil composition exhibits a traction coefficient of about 0.0191 or less as measured by a 16N / 100 ° C./30 SSR value. The method according to any one of claims 1 to 6, Wherein the lubricating oil composition exhibits a Brookfield viscosity of less than or equal to about 21,000 cP, a flash point of greater than or equal to 230 ° C. and a NOACK volatility of less than or equal to 15% at −40 ° C. The method according to any one of claims 1 to 6, Wherein the lubricating oil composition exhibits a CCS viscosity of about 3,600 cP or less at -25 ° C. The method according to any one of claims 1 to 6, Wherein the lubricating oil composition exhibits a CCS viscosity of about 3,400 cP or less at -25 ° C. The method of claim 7, wherein Lubricant composition has a traction coefficient of about 0.0191 or less, a Brookfield viscosity of about 21,000 cP or less at -40 ° C, a CCS viscosity of about 3,400 cP or less at -25 ° C, and 230 ° C or less as measured by a 16N / 100 ° C / 30 SSR value. A flash point of 13% and a NOACK volatility of up to 13%. The method of claim 14, The ester comprises about 5 to 15 weight percent of the lubricating oil composition and has a kinematic viscosity of about 2.5 to 4.5 mm ² / s at 100 ° C. The method of claim 9, The ester comprises about 8-12 wt% of the lubricating oil composition and has a kinematic viscosity of about 2.5-4.5 mm ² / s at 100 ° C. The method according to any one of claims 1 to 6, Wherein the lubricating oil composition does not contain a viscosity index improver. About 20 to 75 weight percent of polyalphaolefin fluid having a kinematic viscosity of about 2 to 10 mm ² / s at 100 ° C., about 5 to 40 weight percent of polyalphaolefin fluid having a kinematic viscosity of about 150 to 3000 mm ² / s at 100 ° C., About 10 to 40 weight percent polyalpha olefin fluid having a kinematic viscosity of about 20 to 100 mm ² / s at 100 ° C., at least one polyol ester having a kinematic viscosity of about 2 to 5 mm ² / s at 100 ° C. and a pour point of at least −25 ° C. or About 5 to 20 weight percent diester, and additionally contains one or more gear oil performance additives, Having a kinematic viscosity of 9 to 12.5 mm ² / s at 100 ° C., a traction coefficient value of less than or equal to about 0.0197 when measured as a 16N / 100 ° C./30 SSR value, a Brookfield viscosity of less than or equal to about 26,000 cP at −40 ° C., −25 CCS viscosity below about 4200 cP, flash point above 220 ° C and NOACK volatility below 15% Lubricating oil composition, characterized in that. The method of claim 18, PAO fluid having a kinematic viscosity of about 3.5 to 8 mm ² / s at 100 ° C. about 30 to 60% by weight, PAO fluid having a kinematic viscosity of about 150 to 1500 mm ² / s about 5 to 20% by weight, about 20 to 80 mm at 100 ° C. PAO fluids of about 15 to 30% by weight, the ester oil include about 5 to 15% by weight having a kinematic viscosity of about 2 to 4.5mm ² / s at 100 ℃, and one or more additional performance additives in gear having a kinematic viscosity of ² / s Lubricating oil composition containing. The method of claim 18, A lubricant composition comprising about 30 to 60 weight percent of a PAO fluid having a kinematic viscosity of about 2 to 10 mm ² / s at 100 ° C. The method of claim 18, A lubricating oil composition comprising about 5 to 20% by weight of a PAO fluid having a kinematic viscosity of about 150 to 3000 mm ² / s at 100 ° C. The method of claim 18, A lubricant composition comprising about 15 to 30% by weight of a PAO fluid having a kinematic viscosity of about 20 to 100 mm ² / s at 100 ° C. The method of claim 18, The lubricant comprises about 5 to 15 weight percent of the lubricant composition and has a kinematic viscosity of about 2 to 4.5 mm ² / s at 100 ° C. The method according to any one of claims 18 to 23, About 45 to 55% by weight of PAO fluid having a kinematic viscosity of about 3.5 to 6 mm ² / s at 100 ° C., about 8 to 12% by weight of a PAO fluid having a kinematic viscosity of about 150 to 500 mm ² / s at 100 ° C. and at 100 ° C. A lubricant composition comprising about 18 to 22% by weight of a PAO fluid having a kinematic viscosity of about 20 to 60 mm ² / s. The method of claim 24, A lubricant composition wherein the ester is a non-polyol ester. The method of claim 25, The non-polyol ester comprises about 5 to 15 weight percent of the lubricating oil composition and has a kinematic viscosity of about 2.5 to 4.5 mm ² / s at 100 ° C. The method according to any one of claims 18 to 23, A lubricating oil composition, characterized by a traction coefficient of less than about 0.0191 as measured by a 16N / 100 ° C./30 SSR value. The method according to any one of claims 18 to 23, A lubricating oil composition characterized by a Brookfield viscosity of less than or equal to about 21,000 cP at -40 ° C, a flash point of greater than or equal to 230 ° C, and a NOACK volatility of less than 15%. The method according to any one of claims 18 to 23, A lubricating oil composition, characterized by a CCS viscosity of about 3,600 cP or less at -25 ° C. The method according to any one of claims 18 to 23, A lubricating oil composition characterized by exhibiting a CCS viscosity of about 3,400 cP or less at -25 ° C. The method of claim 24, A traction coefficient of about 0.0191 or less, a Brookfield viscosity of about 21,000 cP or less at -40 ° C, a CCS viscosity of about 3,400 cP or less at -25 ° C, a flash point of 230 ° C or less, as measured by a 16N / 100 ° C / 30 SSR value, and A lubricating oil composition, characterized by a NOACK volatility of less than 13%. The method of claim 31, wherein The lubricant comprises about 5 to 15 weight percent of the lubricant composition and has a kinematic viscosity of about 2.5 to 4.5 mm ² / s at 100 ° C. The method of claim 26, The lubricant comprises about 8 to 12 weight percent of the lubricant composition and has a kinematic viscosity of about 2.5 to 4.5 mm ² / s at 100 ° C. The method according to any one of claims 18 to 23, A lubricant composition comprising no viscosity index improver.